Vinylcyclohexene hydrochlorides



March 7, 1950 H. JOHNSON ET AL 2,499,505

l VINYLCYCLOHEXNE HYDROCHLORIDES Filed Nov. 2o, 1945 unreacted 1 Patented Mar. 7, 195() 2,499,505 VINYLoYcLonEXEmi HYDROCHLORIDES Media, and .Archibald P.

.Herbert L. Stuart,

Company, y New Jersey Johnson,

Application November Norwood, Paz,

Philadelphia,

assignors` to Sun Pa., a corporation of 1945, serial No. 629,806

2 Claims. (Cl. 26o- 648) This invention relates tothe preparation of novel 1-vinylcyclohexene-3 derivatives, particularly those obtained upon the. of 1-vinylcyclohexene-3.

According to the invention 1`viny1cyclo hexene-S is contacted with aqueous concentrated hydrochlorination l hydrochloric acid at a temperature within theY range C.120

1-vinylcyclohexene-3 dihydro- -vinylcyclohexene-3 and. The mixture thus hydrochloride, chloride, any unreacted 1 aqueous hydrochloric acid. formed is treated to separate therefrom.

Depending upon the conditions employed, a

C. for a time sucient to form a mixture containing 1-Vinylcyclohexene-.3 mono.

the desired productU I vinylcyclohexenepreponderant proportion of l-vinylcyclohexene-B monohydrochloride can be made to form in the reaction mixture or a preponderant proportion of 1-viny1cyclohexene-3 dihydrochloride can be made to form in the reactionmixture. When 1-vinylcyclohexene-3 monohydrochloride sired as the final product, any unreacted l cyclohexene-3 can be' recycled for further hydrochlorination. When vl-vinylcylohexene-i dihydrochloride is desired as the final product, any

-vinylcyclohexene-3 -and 1-vinylcycl0- hexene-3 monohydrochloride canbe. recycled for further hydrochlorination.

As stated, depending upon the conditions mployed a preponderant proportion of Yl-vinylcyclohexene-3 monohydrochloride or a preponderant proportion of l-vinylcyclohexeneride will be formed.

The conditions-for the formation of 1-vinylcyclohexene-3 monohydrochloride are as follows: The temperature ,at which hydrochlorination is effected should be. Within inerente 15 .C.-120. C., preferably 55 C.15 C. Concentrated hydrochloric acid, about 12 norma should be used. Vigorous agitation is required to ensure intimate contact between 1-vinylcyclohexene-3 and the acid solution. It has not been found possible, within the stated temperature range, to hydrochlornate l-vinylcyclohexene-3 with anhydrous hydrogen chloride. Accordingly, a specic characteristic of the reaction of this invention is that it must be carried out employing a hydrochloric acid solution.

The volume ratio of hydrochloric acid to 1- vinylcyclohexene-3 employed will. of course, de-

is de- -Vinyll drochloric acid,

pend upon the concentration of the acid. When about 12 normal hydrochloric acid is employed the volume ratio will be about 0.64.

The conditions for the formation of 1-vinylcyclohexene-3 dihydrochloride are as follows:

The temperature at Which hydrochlorination iseiiected should be within the range 50 C.120 C., .preferably 75 C.-110 C. Concentrated hyused. Vigorous agitation is required to ensure intimate contact between 1 viny1cyclohexene3 and acid solution.

The volume ratio lof hydrochloric acid to 1- 3 will, of course, depend upon the concentration of the acid. When about 12 normal hydrochloric acid is employed the volume ratio will be about 5.15.

The reaction time will vary depending upon conditions of the operation employed. For example, at higher temperatures, Within the stated ranges, the reaction appears to proceed more rapidly. Also, an increase of pressure appears the rate of the reaction. Further- 1 more, vigorous agitation Will aid in reducing the Aing a hydrochloric acid solution,

' reaction time.

"'tity of w of about three hours has been required for completing substantially the desired reaction.

Although the reaction is to be effected employfor example, aqueous hydrochloric acid, it is to be understood that hydrogen chloride gas may be fed to a reactor containing l-vinylcyclohexene-S and water forming the hydrochloric acid in situ. The quanater present can vary greatly. tities of water present ranging from about 5% to about v% of the total reaction mixture have been employed. Alcohol, ether or other compatible solvent can be employed to prepare the hydrochloric acid solution.

By proceeding as detailed above, employing 1- vinylcyc1ohexene3, a monohydrochloride of 1- vinylcyclohexene-3 or a dihydrochloride of vinylcyclohexene can be obtained. The products oi the invention are Water white liquids. 1vinyl cyclohexene-3 monohydrochloride has a boiling point of C.87 C.at 38 mm. Hg and a refractive index of 1.4796 nD2C. l-vinylcyclohexene-S dihydrochloride has a boiling point Within the .point of 85 C.87 C.. at 38 mm. Hg and a refracabout 12 normal, should be Quan- Ratio and as intermediates for further chemical reac tion.

It will be understood to those versed in the art that variation and modification are possible within the spirit of the invention the essence of which is that new derivatives of 1vinylcyclohexene3 have been obtained, particularly hydrochlorides of l-vinylcyclohexene-S, and that a process for the preparation of these compounds by hydrochlorination of l-vinylcyclohexene-3, under the specific conditions and in the manner aforesaid, have been set forth.

Recycle Yield, Per Cent (,255) b' 2Q/liter Y .m vonr vvcnnci -vcn.2Hc1 voiHci voH.2Hc1 VCH-2HC1 Rxk 2.0 65 5 12 1.79 29.7 43.6. 26.7 62.0 38.0 1.0 1.0 65 5 12 1.29 64.4 26.1 9.15 72.8- 27.2 2.7 0.5 65 5 12 0.644 80.1 15.9 4.0 80.3. 19.7 4.1 0.5 90 5 12 0.644 74.3 18.0 7.7 70.8 29.7 2.4 I 0.5 65 2.5 12 0. 644 88.0 5.8 6.2 40.7 50.3 1.0 0.5 65 5 9 0. 644 89.9 6.4 3.7 63.5 36.5 1.7 y l M In the drawing there is shown, schematically, a 1 We claim: ow plan of apparatus which can be employed for l. A process for the preparation of the monothe continuous production' of l-vinylcyclohexe hydrochloride of 1-.vinylcyclohexenef3:which comene-3 monohydrochloride and/o1 l-vinylcyclohexpl'l'SeS COnlaCing, With Vl'gOIOUS agtallOn 1 ene-3 dihydrochioride, as desued The cond1- vinylcyclohexene-B Wlth about 12 normal aqueous tions of operation and the quantities of reactants hydrochloric acid for from about 2.5 to about 5 employed are as above detailed hours while maintaming the reaction mixture at l-vinylcyclohexene-3 and 12 normal hydrochloa temperature of from .about 55 C. to about 750 C., ric acid solution are fed to the reactor until the thereactants beingpresentinan amountsueh that same is about 2/3 full. Agitation is begun and the the volume ratioA of said hydrochloric acid to said contents of the reactor is raised to the desired..35 l-VnylGyClOheXf-rle-31'Saboutllndsepalatng temperature which is maintained until the rethe monohydrochloride. of 1-vinylcyclohexene-3 action has been substantially completed At this from the reactionl mixture. stage, the reaction products are fed tothe separa- 2. A process for' the preparation 0f the monotor While additional quantities of l-vinylcyclohex hydrochloride of 1vinylcyclohexene3 which ene3 and hydrochloric acid solution are fed to .40 with vigorous agitation, 1-

the reactor. actor is maintained about 2/3l full and sc that the reactants will remain 1n the reactor for the deconsistency and appear to be useful as 'plasticizers- The ilow is regulated so that the rein the event it is the is recycled to the rey REFERENCES CITED The following references are, of record` in the le of this patent.'

Y U'rnrisnl STAT-Es- PATENTS Number Name Date 2,401,414 Doumani etal. June 4, 1946 FOREIGN PATENTS l Number Country Datey 268,722', Germany 1 Dec. 29, 1913 343,116 Great-Britain Feb. 16, 1931 Certiicate of Correction Patent No. 2,499,505 March 7, 1950 HERBERT L. JOHNSON ET AL.

It is hereby certiied that errors appear in the printed specieation of the above numbered patent requiring correction as follows:

Column 2, line 50, strike out "point of 85 O.-87 C. at 38 mm. and insert instead range 85 @-1100 U. at 10 mm.; column 4, line 82, for 750o C. read 75 U.;

and that the said Letters Patent should be read With these corrections therein that f the same may conform to the record of the oase in the Patent Oice. Signed and sealed this lst day of August, A. D. 1950.

[smi

THOMAS F. MURPHY,

Assistant yommz'ssz'oner of Patents. 

1. A PROCESS FOR THE PREPARATION OF THE MONOHYDROCHLORIDE OF 1-VINYLCYCLOHEXENE-3 WHICH COMPRISES CONTACTING, WITH VIGOROUS AGITATION, 1VINYLCYCLOHEXENE-3 WITH ABOUT 12 NORMAL AQUEOUS HYDROCHLORIC ACID, FOR FROM ABOUT 2.5 TO ABOUT 5 HOURS WHILE MAINTAINING THE REACTION MIXTURE AT A TEMPERATURE OF FROM ABOUT 55*C. TO ABOUT 750 C., THE REACTANTS BEING PRESENT IN AN AMOUNT SUCH THAT THE VOLUME RATIO OF SAID HYDROCHLORIC ACID TO SAID 1-VINYLCYCLOHEXENE-3 IS ABOUT 0.64, AND SEPARATING THE MONOHYDROXHLORIDE OF 1-VINYLCYCLOHEXENE-3 FROM THE REACTION MIXTURE. 